AU616166B2 - Biostatic and biocidal compositions - Google Patents
Biostatic and biocidal compositions Download PDFInfo
- Publication number
- AU616166B2 AU616166B2 AU10864/88A AU1086488A AU616166B2 AU 616166 B2 AU616166 B2 AU 616166B2 AU 10864/88 A AU10864/88 A AU 10864/88A AU 1086488 A AU1086488 A AU 1086488A AU 616166 B2 AU616166 B2 AU 616166B2
- Authority
- AU
- Australia
- Prior art keywords
- acrolein
- biostatic
- polymers
- polymeric
- biocidal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000002599 biostatic effect Effects 0.000 title claims abstract description 35
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- -1 hydrated Chemical class 0.000 claims abstract description 7
- 150000002373 hemiacetals Chemical class 0.000 claims abstract description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 102
- 239000000758 substrate Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
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- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
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- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 239000004567 concrete Substances 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002537 cosmetic Substances 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 239000011953 free-radical catalyst Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 239000000919 ceramic Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 3
- 101150065749 Churc1 gene Proteins 0.000 claims description 3
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 241000589516 Pseudomonas Species 0.000 description 10
- 230000000845 anti-microbial effect Effects 0.000 description 10
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- 229960003328 benzoyl peroxide Drugs 0.000 description 9
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- MCIPQLOKVXSHTD-UHFFFAOYSA-N 3,3-diethoxyprop-1-ene Chemical compound CCOC(C=C)OCC MCIPQLOKVXSHTD-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 239000010941 cobalt Substances 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
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- OZUXTDPAPUKZKA-UHFFFAOYSA-N 1-acetylperoxyprop-2-enyl ethaneperoxoate Chemical compound CC(=O)OOC(C=C)OOC(C)=O OZUXTDPAPUKZKA-UHFFFAOYSA-N 0.000 description 1
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- HLHVCCRWRZJHQL-UHFFFAOYSA-N 3,3-diethoxyprop-1-ene prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C)OC(C=C)OCC HLHVCCRWRZJHQL-UHFFFAOYSA-N 0.000 description 1
- 208000030507 AIDS Diseases 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000223651 Aureobasidium Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
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- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FSSWLSLBJRLZJE-UHFFFAOYSA-N methanol;prop-2-enoic acid Chemical compound OC.OC(=O)C=C FSSWLSLBJRLZJE-UHFFFAOYSA-N 0.000 description 1
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 235000019319 peptone Nutrition 0.000 description 1
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- 239000006215 rectal suppository Substances 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/34—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Medicinal Preparation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Materials For Medical Uses (AREA)
Abstract
PCT No. PCT/AU87/00435 Sec. 371 Date Jul. 31, 1989 Sec. 102(e) Date Jul. 31, 1989 PCT Filed Dec. 21, 1987 PCT Pub. No. WO88/04671 PCT Pub. Date Jun. 30, 1988.Polymeric compounds having a polyacrolein sub unit in aldehyde, hydrated, hemi acetal or acetal form are provided which have biocidal or biostatic properties. The polymeric compound may be used to treat, or be included in, a wide range of products.
Description
I
61 66 Ub 6 ll WORLD INTELLECTUAL PROPERTY ORGANIZATION !nternational Bureau Is INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 International Publication Number: WO 88/ 04671 CO8F 116/34, 116/38, 220/06 Al A01N 35/02 (43) International Publication Date: 30 June 1988 (30.06.88) (21) International Application Number: PCT/AU87/00435 (74) Agent: EDWD. WATERS SONS; 50 Queen Street, Melbourne, VIC 3000 (AU).
(22) International Filing Dat 21 December 1987 (21.12.87) (81) Designated States: AT (European patent), AU, BE (Eu- (31) Priority Application Number: PH 9657 ropean patent), BR, CH (European patent), DE (European patent), DK, FI, FR (European patent), GB (32) Priority Date: 23 December 1986 (23.12.86) (European patent), HU, IT (European patent), JP, KR, LK, LU (European patent), NL (European pa- (33) Priority Country: AU tent), NO, RO, SE (European patent), SU, US.
(71) Applicant (for all designated States except US): BIOPO- Published LYMERS LIMITED [AU/AU]; 63 Thompson Road, With international search report.
North Fremantle, W.A. 6159 (AU).
(72) Inventors; and A.O.J.P. 1 8 AUG 1988 Inventors/Applicants (for US only) MELROSE, Graham, John, Hamilton [AU/AU]; 20 Nardina Crescent, Dalkeith, W.A. 6009 KLEPPE, Conce'lta, Maria AUSTRALIAN [AU/AU]; 39 Ellam Street, Bentley, W.A. 6102 (AU).
LANGLEY, Jeffrey, Wayne [AU/AU]; 25 Portcullis 15 JUL 1988 Drive, Willetton, W.A. 6155 STEWART, Jr"frey, Mark [AU/AU]; 17 Lambert Street, Alfred Cove, PATENT OFFICE W.A. 6154 VAN DYK, Jacobus [NL/AU]; 11 Werndley Street, Armadale, W.A. 6112 (AU), (54) Title: BIOSTATIC AND BIOCIDAL COMPOSITIONS (57) Abstract Polymeric compounds havin, a polyacrolein sub unit in aldehyde, hydrated, hiemi acetal or acetal form have biocidal or biostatic properties. The polytieric compound may be used to treat, or be included in, a wide range of products.
i
I
RECEIVED 2 2JUL 1988 PATENT COOPERATION TREATY APPLICATION NO. PCT/AU87/00435 BIOPOLYMERS LIMITED DEMAND ATTACHED SHEET BOX NO. IV.
In response to the International search report the specification and claims have been amended to clearly describe the invention and to clearly distinguish the present invention from the prior art cited.
The specification has been extensively revised without broadening the scope of the specification beyond that of the original disclosure. Applicant requests that the revised specification annexed hereto be substituted for the specification orginally lodged.
__I
-1- BIOSTATIC AND BIOCIDAL COMPOSITIONS The present invention relates to a process of rendering matter blocidal or biostatic and to polymeric and biocidal compositions of matter formed therewith and relates particularly but not exclusively to polymeric acroleln biocidal or biostatic compounds and to substrates or substrate materials treated therewith.
As is well known a biocidal substance kills microorganisms and a blostatic substance inhibits the growth of microorganisms; microorganisms including for example, bacteria, fungi and viruses. It is also known that aldehydes such as glutaraldehyde and formaldehyde are biocidal or biostatic and that substrates or substrate materials may be treated with such substances or compositions to render them at least temporarily biocidal or biostatic. The disadvantages of the use of such substances or such compositions is that the aldehydes have penetrating, obnoxious odours and are volatile thus rendering them unsuitable for long term biocidal or biostatic treatment of substrates or substrate materials.
As a result of microbial action, untreated substrates or substrate materials may be subject to deterioration or production of odours of formation of obnoxious or slippery slime or mildew or give rise to inflammation or transfer of disease. Thus, it is desirable that such substrates or substrate materials can be treated to render them biocidal or S biostatic.
Another disadvantage of such conventional biostatic or biocidal compounds or compositions is that they are relatively low molecular weight and therefore pass relatively freely through biological membranes such as the skin or the intestinal wall and in both cases, into the blood stream of humans or animals where they may give rise to antigenic, allergenic or S toxic effects; similar destructive or toxic results may arise from for example, passage through the roots or outer membranes of fruits or vegetables. Thus, there is a need for biostatic or blocidal 8w KNK:861y
A
V T -2compounds or compositions which do not readily pass through biological membranes.
Prior art such as French Patent 1312166, British Patent 946663 and U.S. Patents 3635898 and 4016127, for example, disclose methods of polymerising acrolein for various purposes such as in the treatment of leather to provide improved mechanical properties. However no prior art recognises that such polymers or polymerisation reactions provide biostatic or biocidal properties to substrates treated by such polymers or polymerization i0 processes or that any polymers so produced have biostatic or biocidal properties.
Kirk-Othmer "Encyclopaedia of Chemical Technology" (Third Edition) volume 13 Wiley-Interscience (New York) and "Encyclopaedia of Polymer Science and Technology" Volume 2, 1965 Interscience Publishers (New York) similarly do not refer to any known biostatic or biocidal properties of acrolein polymers or substrates treated with such polymers.
Kirk Othmer refers to the anti fungal or anti slime properties of acrolein monomer. However there is no suggestion that any acrolein polymer may have similar properties. Kirk Othmer also states that no commercial uses are known for acrolein polymers.
Further prior art Journal of Polymer Science Vol 9, 1971, 1013-1025, Ishavov, Azizov, Negmankhodzhayeva and Usamov discloses treatment of cellulose with acrolein to improve mechanical properties of the cellulose. The authors conclude that "no acrolein homopolymer is formed in the vapour systems." and that the footnote to the relevant table S 8 refers to the crosslinking having been done in the vapour phase. This excludes any conclusion that the antimicrobial property relates to polyacrolein polymer; the total context of the paper is of cross-linking in the absence of polyacrolein polymer, being due to monomeric joining of' cellulose by the double bond and the carbonyl group, respectively of acrolein monomer.
,PL.V: i ~I _1 *i 7 RE:CE;Vf 2 ;.E8S S- 3- It has now been discovered that polymeric compounds having, illustratively, the repeating unit CH, CH CH 2 H CHO HO may be utilized as biocidal or biostatic compounds and for the treatment of substrates or substrate materials to render them biocidal or biostatic. However, it is stressed that such polymeric compounds having this repeating unit do not exist at equilibrium, entirely in these iliustrated open chain forms in which the aldehyde groups are entirely un-associated. Specifically, we have discovered that polymers or copolymers of acrolein or of an aldehydederivative of acrolein may be utilised as biostatic or biocidal compounds and for the treatment of substrates or substrate materials to render them biostatic or biocidal.
The invention lies in the recognition of the similarities in structure'between glutaraldehyde, which is a known bacteriostat and bacteriocide, and polymers or copolymers of acrolein or of an aldehyde-derivative of acrolein. In the case of polyacrolein, for example, at equililbrium the structure takes on a number of different forms; it is generally agreed Bergman, W.T. Tsatsos and R.F. Fischer, J. Polymer Sci: Part A, 1965, 3485; R.C.
Schulz, Vinyl Polym., 1967, 1, 403; L. Hunter and J.W.
Forbes, J. Polymer Sci: Part A, 1965, 3, 3471 that sub-units of polyacrolein produced by a free radical inducing agent have the structure.s below R=H): S CH CH -CH CH CH RO" "OR HO0 OH (b) D i..n I yi i; 4
CH
CH
HOD
CH
CH
/,CH
H
H/
0 HO
CH
H C C H2 x integers of 1 or more S in which either the form or the tetrahydropyran ringform or the 13 fused tetrahydropyran ring-form predominate. 3 C-NMR analysis of *too polyacrolein produced by a free radical Inducing agent (free radical catalyst) showed negligible aldehyde carbon, which is consistent with the above structures; the spectrum also showed a number of aliphatic CH's and CH2's and a number of O-CH-O's which are all expected from the above variety of structures.
In keeping with proposals of R.C. Schulz, Vinyl Polym., 1967, 1, 403, 13 D the C-NMR spectrum of polyacrolein produced by an ionic catalyst is consistent with the above structures for the polymer and additionally, the presence of structures and
S
S
0
CH
CH= CH 2 CH -CH 2 Ci\CH H 2 O 1CH
SCH
HO
H
CH-CH
I I CH CH 0C CH =CH CH HO OH KWK:861y 5 The 13 C-NMR spectrum of a copolymer of acrolein diethylacetal acrylic acid was consistant with the polymer having repeating units illustrated by R =CH 3 CH 2 Glutaraldehyde is proposed to exist in the following forms (A.D.
Russell and D. Hopwood, "Progress in Medicinal Chemistry", Vol. 13, Eds.
G.P. Ellis and G.B. West, North Holland Publishing Company, 1976): 6SS@
S
5*s
S.
@6 6SSe 5* S S 6@ *5*S
S
SSSS@@
6 CHE1 CH, CHO CHO (a) CH2 H CH2
(C)
EQ H (b) CE C H 1 2 2 H O- 0 H (d) *set a6S toS @6 @6 S S
S
S
6S*SSS S 6 1H 2
C
2 C H 1 22
CEHE
0 1-1 J y x,y,z =integers of 1 or more KWK:861Y 1
UL-
I 988 6 The '1C-NMR analysis of glutaraldehyde showed that very little of the glutaraldehyde (less than existed in the free aldehyde form There were many aliphatic CH 2 resonances evident in the spectrum with the major peaks numbering eleven. There were also many O-CH-O resonances with nine major peaks. This supports the existence of the above cyclic structures as the linear forms of glutaraldehyde would not give rise to so many different resonances.
According to our invention, an added advantage of these polymers or copolymers of acrolein or of an aldehydederivative of acrolein is that their hydrophilicity/hydrophobicity or water solubility/oil or lipid solubility may be widely adjusted by the inclusion or exclusion, respectively, of hydrophilic comonomers, for example, acrylic acid, vinyl pyrrolidone, vinyl or acrylic monomers containing oxygen-containing groups for example, hydroxyl groups, or ether groups or carboxyl groups, or other similar hydrophilic monomers which will now be apparent to those skilled in the art. Normally, the homopolymers of acrolein are water-insoluble and are thus suited to applications where their elution by aqueous media are not desirable as in sprays for agricultural or veterinary purposes or in applications where the utility of the polyacrolein is sought in oil phases such as some cosmetic/toiletry preparations or foods or engine oils; alternatively, the inclusion of a high percentage of hydrophilic comonomer for example, acrylic acid renders the resulting copolymer suited to use in hydrophilic media which is more usual in cosmetics, toiletries, pharmaceuticals or food substances. Waterdispersable or water-soluble copolymers of acrolein, for example, the 90:10 acrylic acid: acrolein copolymer is especially suited as a sterilent, sanitiser, antimicrobial or preservative in cosmetics, toiletries, pharmaceuticals or food substances. A particular application which we record is that we preject copolymers of acrolein or of a carbonylderivative of acrolein Iiay be dissolved in an aqueous i: C--l ii-i: -;il i ii 7 solution or in a gel-like medium formed through, for example, the presence of carboxymethylcellulose and then the resulting solution or gel used as a rectal suppository to combat the transmission of AIDS virus amongst homosexuals.
Also the solution or gel could be enclosed in a small tube (as toothpaste is conventionally dispensed) the cap of the tube'incorporating a syringe-needle which is made available to drug addicts who are in danger of transmitting AIDS through unclean injection-techniques; of course, the storing of the syringe-needle in the solution or gel would have a biostatic or biocidal effect against the aids microorganism.
A further advantage of the said polymers or copolymers of acrolein or of a derivative of acrolein is that their biostatic pr biocidal activities appear to be less pH-dependent than glutaraldehyde (see S.D. Rubbs et al., J. Appl. Bact., 1967, 30(1), 78).
An advantage of using an aldehyde-derivative of acrolein is absence or greatly reduced acrid smell, compared with acrolein, during the polymerization. Of course, however, all final polymers and even those prepared from acrolein are essentially odour-free.
Substrates which can be treated with the compounds of the invention include cellulose, modified cellulose, regenerated cellulose, rayon, natural or synthetic polymers of thermo-setting or thermo-plastic materials, natural or synthetic fibres or resins including such as vinyl polymers, acrylic polymers, polyamides, polyesters, rubbers and various materials such as surface coatings, ceramics, glass, concrete, wood, masonry, metals, minerals and earths.
Examples of substrate materials which may be made by such substrates are: Airconditioner filters, line wipes, aprons, bags for laundry, bandages or adhesive bandages, bathroom tiles or grout, bricks, car or other carpets, catheters and related hospital instruments made from plastic or glass, clothing including underwear, cloth wraps for food, concrete, cotton- ".4 1 i i I; 3 S.198 8 balls or cotton tips (buds), diapers, disposable towels, drapes (domestic, commercial, industrial or hospital), disposable cardboard or plastic food boxes, face masks (hospital or industrial) bed covers, inners of shoes, ironing board covers, jumpers or cardigans, nursing pads, paint for ships' hulls or underwater pylons, paper plates and cups, water reservoirs or swimming pools or watertreatment chemicals, rubbish bins made from cardboard or plastic, sanitary napkins or feminine hygiene tampons, 1sheeting for babies' or incontinent persons' beds, shelving paper, shower curtains, socks, sterile gloves, sterile overalls, teatowels, telephones diaphragms for mouth pieces, tents, tissues, handkerchiefs, toilet paper, toothbrush nylons, towels, wall paper, window awnings or other like structures made from canvas plastic etc., wipes, mop.s, sponges, wood or wood-impregnants.
It has now also been discovered that polymerization of acrolein or an aldehyde-derivative of acrolein, with or without other comonomer in the presence of a substrate or substrate material causes the polymer to chemically bond to the substrate such as through graft polymerization. This has the advantage that the biocidal or biostatic agent is not readily removed from the substrate. Thus, the effect of the biocidal or biostatic agent may be longer-lasting than Sin cases where there is no chemical bond.
The rendering of the substrate biocidal or biostatic either prevents microbiological degradation of the substrate, prevents the production of odours which may result from degradation of the substrate or from the degradation of chemical compounds contained in or within the substrate. This rendering also prevents the substrate from being a vector of inflammation or disease. Further, mould, lichen oL other similar formation on the substrate may be prevented. The biostatic or biocidal agent of the-'present invention may be associated with materials from which substrates are made, so as to be incorporated into the final product or alternatively, the finally fabricated substrate F A. (T 4 r r -9.
may be suitably treated to associate it with the biocidal or biostatic agent.
According to a first embodiment of the invention there is provid process for rendering matter blocidal or biostatic, which process compi applying to or incorporating in the matter a biocidally or biostatcaI effective amount of a polymer compound havin~g the polyineric unit
CH
2
-CH-CH-CH-
C;HO CHO or this unit in a hydrated, hemi-acetal or acetal form of the formulae CH
CH
I I. I, IO a so (b) ease F1
CRH
*CH
CH
i ~ntegers of I or more H *0 0 a. CH C ed a ri ses ly C H C 2 CH H Cli"H0 CHi 0 CH CH Ho 0
N
0
O
Mf KHK:861y wherein R is hydrogen and x is an integer of 1 or more; or a composition containing said polymeric compound.
Such a biostatic or biocidal compound having the repeating unit(s) as shown above is derived from a polymer or copolymer of acrolein or of an aldehyde-derivative of acrolein.
According to a second embodiment of the present invention there is provided a polymeric biocidal or biostatic composition comprising a biocidally or biostatically effective amount of a polymer compound havinqr the polymeric repeating unit
CH
2
-CH-CH-CH-
IH IH 0O8S *9 9 0S**
OS
S S
S.
0 OSSe
S
S
a 9 Set eq
S
e.g.
C.
9* S 5! 9 S 9 S. eq S 0 4**SSe 9 or this unit in hydrated, hemi-acetal or acetal form of the formulao Cu cmH CH cH HO 0 (b X=iotegers, ot O mo~ Ie
C)
CH
O
CH
2 KWK:fl6ly i ~~i(i 10A o CH 12 CH- CH CH CHCH CH I2 2 CH. H O C /CH H 0CH O I "CH" CH CH 0 wherein R Is hydrogen and x is an integer of 1 or more, or a composition containing said polymeric compound; incorporated in or bound to a substrate or substrate material.
"Sa. 5 Such a composition comprises a blostatic or biocidal compound having the repeating unit(s) as shown above and being derived from a polymer or copolymer of acrolein or of an aldehyde-dervative of acroleln bound to a substrate or substrate material, According to a third embodiment of the present invention there is provided a process of preparing the composition according to the second embodiment comprising polymerizing acrolein or a derivative thereof in the presence of the substrate or substrate material, Preferably the polymerization is performed in the presence of a polymerization inducing agent. The polymerization inducing agent is either a free-radical initiator, or an ionic initiator, An example of a polymerization inducing agent that can be used with the present invention include an ionic catalyst, gamma radiation, a free radical catalyst, ultraviolet radiation or electron beam radiation or a combination thereof. Preferably the polymerization inducing agent is gamma radiation such as is produced by a radioactive cobalt source, A process for preparing a polymer biocidal or bios',atic polymer compound EH/KXW:1453y
L
10B for use in the present invention comprises polymerizing acAlein monomer or a derivative thereof in the presence of a polymerization promotor selected from a free radical catalyst or ionic catalyst, gamma radiation or electron beam radiation.
For the free radical polymerization process preferably the polymeri~Ltion is carried out, at reflux, for a period of from 2 minutes to 100 hours, prefe bly from 5 minutes to 48 hours in the presence of a solvent selected from water a lower alkanol or mixtures thereof. Preferably the polymerization is effected by heating a solution of acrolein, one part by weight, in the solvent, 250 parts by weight, at the reflux temperature of the solvent and under .i .nitrogen in the presence of a catalyst. More preferred, the catalyst 15 is present in an amount of from 0.001 to 0,1 parts by weight.
For the ionic polymerization process, preferably the catalyst is .an ionic catalyst and preferably the acrolein monomer is in the form of a 0.25 50% w/w solution of acrolein, preferably redistilled, in water and, the catalyst is a solution, pH 9-13, effected by the addition of an alkali hydroxide in water, the process being effected with stirring at room temperature for a period of from 2 minutes to 48 hours, Preferably the solution of an alkali hydroxide is 2M sodium hydroxide.
SFor the process in the presence oF gamma radiation, preferably the acrolein monomer is in the form of a 0,25 50% w/w solution in a lower alkanol, preferably methanol which is subject to gamma radiation (0.01 M rad/hr 10 M rad/hr) for from 5 minutes to 48 hours; When the polymerization is carried out in the presence of a substrate it is preferably a cellulosic substrate and preferably the substrate is soaked or suspended in a 1-75% w/w solution of acrolein in a lower alkanol, preferably methanol, and subject to gamma radiation (0.01 M rad/hr 10 M rad/hr) for from 5 minutes to 48 hours.
1453y SRECEiVED 2 2 JUL 18 11 The compound or compositions of the invention or produced by the processes of the invention may be used as an antimic-obial or preservative for water, water-containing compositions, food, cosmetics, toiletries, pharmaceuticals, or oils or lubricants; as an antimocrobial, sterilent, antimicrobial, antiseptic, disinfectant or sanitiser in industrial, agricultural, veterinary or human health-care applications; or as a solid liquid, solution, emulsion, suspension or gel, including such applications as for specific use against viruses and such related microorganisms in the form of a solid, liquid, solution, gel, emulsion or suspension of matter.
The invention also provides a method of producing a Sbiocidal or biostatic composition of matter which comprises polymerizing acrolein or a derivative thereof in the presence of or with a substrate or substrate material preferably in the presence of a polymerization inducing agent. The polymerization inducing agent is preferably selected from gamma radiation, such e,3 is produced by a radioactive cobalt source. The present invention also relates to methods of rendering substances or compositions biocidal or biostatic and to uses of such biocidal or biostatic substances or compositions. The invention also Srelates to the uses of polymeric compounds as herein described to render substances or compositions biocidal or biostatic.
The invention will now be illustrated by the following non-limitative examples.
30 Example 1 Preparations and Structures of Polyacrolein Using a free radical inducing agent (free radical catalyst): 9.64g distilled acrolein and 25g methanol were placed in a 100ml round bottom flask and purged with f nitrogen. 0.525g benzoyl peroxide was added and the solution stirred under nitrogen at 60 degrees centigrade.
The reaction was allowed to continue for a total of ca. 88 j w-ll i u 12 hours. After this time the reaction solution had become strongly yellow in colour and had a solids content of 30.5%.
3 C-NMR (300MHZ) E(relative to d -methanol at 49.00): 33.27 33.53 33.79 33.87 37.03 37.29 37.54 37.64 (CH 2 97.15 103.37 104.34 139.36 (CH); 139.78(CH2); 196.72 The 3C-NMR spectrum shows some residual acrolein with the aldehyde carbon at 6196.72 and the vinylic CH 2 and CH at 6139.78 and 6139.36, respectively; apart from the 6196.72 (CH) resonance absorption, there was no other attributed to -CHO. The spectrum is consistent with polymeric acrolein consisting of fused tetrahydropyran rings and some free dihydroxy methyl groups. The rings exist in either the boat or chair configurations giving rise to more chemical shifts than may be expected.
A similar polymerization of acrolein was also carried out: 25.02g methanol was placed in a reaction vessel fitted with a thermometer, reflux condenser and nitrogen inlet tube. 0.528g of benzoyl peroxide was added and 9.65g of distilled acrolein was added. The system was purged with nitrogen and heated in an oil bath at 60 degrees centigrade with stirring, for 24 hours; when a solids determination indicated 20% conversion; total conversion was 40% after a further 48 hours heating.
Typically, as an indication of molecular weight, the polyacrolein was found to have a retention time which was shorter than that of polyethyleneglycol 10,000 on a Porasil GPC 60 Angstrom column using a Waters Associated Model ALC/GPC 204 liquid chromatograph fitted with a differential rfraictometer R401.
Using an ionic catalyst: 1.6g distilled acrolein was made up to 20ml with deionised water in a 200ml beaker and then, ca. 0.5ml of 0.2M sodium hydroxide addeu with stirring to pH ca. 10-11. The solution became cloudy and a white precipitate began to form. The contents were stirred for a further 2 hours and then filtered. The precipitate was washed thoroughly with delonised water until the U "Is I. Jf<. 1 i, i j EPY L71 I. 'RECEV 2 JJL 1388 -13 filtrate was neutral. The product was dried under vacuum and was a white-pale yellow, fine powder; it readily dissolved in methanol and conveniently and importantly, could be evaporated down to dryness and then again, dissolved in methanol or other solvents. In a similar determination to the above, the polyacrolein was found to have 'a retention time which was shorter than that of polyethylene glycol 10,000. 13C-'MR (300MHz) S(relative to d 4 -methanol at 49.00): 19.-31 (CH 35.95 (CH 37-42 (CH); i0 62-73 (CH 2 73-81 92-95 96-103 114-120
(CH
2 134-141 196.0 (CH).
Example 2 Preparation of 90:10 Acrylic Acid: Acrolein Copolymer 6.489g distilled acrylic acid, 0.56g distilled acrolein and 15g methanol were placed in a 50ml round bottom flask and purged with nitrogen. 0.33g benzoyl peroxide was added and the solution stirred under nitrogen at 60-65 degrees centigrade. The reaction was continued for ca. 66 hours. After this time the contents of the flask had become very viscous, having a solids content of 57.7% (indicating 100% conversion).
A sample of the viscous material was placed on a petri dish and dried on a hot plate to remove solvent.
Drying was completed in an oven at 80 degrees centigrade and a transparent, slightly yellow coloured polymer was obtained. The copolymer is completely soluble in warm water (ca. 50 degrees cehitigrade) and once dissolved remains so, even on cooling the solution.
In order to ensure that the solids obtained were polymeric, a simple dialysis experiment was performed: of an aqueous solution containing 0.65% solids was placed in a dialysis tube. This was irrigated with water continuously for ca. 66 hours. The solution in the dialysis tube was then recovered and the solids content determined at 0.68%.
Since the solids were completely retained and the lower limit for solids penetration through the dialysis tube is 2000 mwt, we conclude that the solids are polymeric L t> 1L iJ-iw.
l I A: U RECEIVED 2 2 JUL 1988 14 Example 3 2.8g of acrolein diethyl acetal was placed in a 100 ml round bottom flask and the contents purged with nitrogen.
A solution of 0.216g potassium persulphate in 7.5g water was added with stirring, under nitrogen. The flask was placed in an oil bath at 60-70 degrees centigrade and stirred for ca. 20 hours. A yellow solid was recovered and dried at degrees centigrade; weight 0.915g.
Examp7e 4 4g distilled acrylic acid, 4.81g acrolein diethyl acetal and 15g methanol were placed in a 50ml round bottom flask and purged with nitrogen. Then 0.3g benzoyl peroxide was added and stirring continued under nitrogen at 60-65 degrees centigrade for 70 hours (solids determination indicated a 50% conversion). 3C-NMR (300MHz) 6(relative to d -methanol at 49.00): 15,.58 (CH 18.31 (CH 35.52 (CH 36\?4 (CH 2 37.07 (CH 42.36 42.85 (CH); 58.32 (CH 130.00 131.57 178.51 (CH).
EXample 3.8g of acrolein diethyl acetal, 3.3g vinyl pyrrolidone and 10g methanol were placed in 50ml round bottom flask and thoroughly purged with nitrogen. 0.71g azobisisobutyronitrile was added and the flask heated in an oil bath at 60-65 degrees centigrade, with stirring under nitrogen for 72 hours when the conversion was 44%. The copolymer was found to be soluble in methanol.
Example 6 In a similar technique to the above, 3.9g acrolein diethyl acetal, 1.16g acrylic acid, 7.5ml water and 0.216g potassium persulphate were heated under nitrogen, with stirring in an oil bath at 60-70 degrees centigrade for ca.
i 24 hours when a white waxy material was recovered; it was insoluble in water, but swelled in methanol, acetone, tetrahydrofaran or methyl ethyl ketone.
j C^E-IT j T '7CE D JUL 15 Example 7 A similar result was achieved through heating and stirring in the usual way to the above: 14.5g methanol, 3.62g distilled acrolein, 1.21g distilled acrylic acid and 0.265g benzoyl peroxide. After 40 hours the conversion was Examples 8-11 A 50:50 mixture of monomers was treated as follows: 2.35g distilled acrolein, 2.88g distilled acrylic acid and 1 14.5g methanol were placed in a 50ml round bottom flask and flushed with nitrogen. 0.2625g benzoyl peroxide was added and after heating at 60-70 degrees centigrade for 48 hours the conversion was 70%. The polymer swelled in methanol but was insoluble in water.
Similar preparations were achieved with different ratios of the monomers acrolein:. acrylic acid namely, 30:70 (Example 10:90 (Example 10), 2.5:97.5 (Example 11). The products from Examples 10 and 11 were soluble in water and retained by dialysis tubing of exclusion 2,000mwt.
Example 12 In a similar preparation to the above, 42% conversion was achieved of a polymer which swelled in methanol or water, from 1.8g acrolein, 3.3g vinyl pyrrolidone and 0.071g azobisisobutyronitrile.
Example 13 benzoyl peroxide was added to a solution of 1.02g polyethyleneglycol acrylate and 0.5ml acrolein in methanol. The mixture was stirred and heated to reflux for 48 hours and gave 90% conversion; the residual oil (1.2g) was chromatographed on Sephadex LH-20 (18g) in methanol.
The structure of the resulting polymer was confirmed by NMR analysis.
Examples 14-19 Whatman 5.5cm filter paper was immersed in the following solutions and irradiated by a cobalt source for 4 hours: i, I Svi \.7
A
N<EiVE- 2 JUL 1988 16 Example Acetyl di~thyl acetal Acrylic Acid Methanol 14 2.0ml Oml 18ml 1.6ml 0.4ml 18ml 16 1.2ml 0.8ml 18ml 17 1.0ml 1.0ml 18ml 18 0.4ml 1.6ml 18ml 19 2.0ml* Oml 18ml Acrolein diacetoxy acetal Filter papers were dried in an oven at 70 degrees centigrade for 30 minutes and weighing indicated the grafting of polymer (These yields were recorded after washing with methanol).
Example A small cellulosic paper disk which is normally used fo filtration i.e. a filter paper, about 2 cms. in diametet was immersed in a 10% solution of acrolein in water ml), contained in a tube. The tube and its contents were flushed with nitrogen, sealed, and then gamma-radiated for one hour from a cobalt source (approximately 0.7 Mrad/hour). The disk was then removed and washed with water.
The following standard strains were used for testing: a) Staphylococcus aureus (Oxford) b) Pseudomonas
ATCC
c) Candida ATCC Dilutions were prepared in normal saline.
lOul of each bacterial solution was applied to 1 square centimetre of test filter paper. Filter papers were maintained in a moist atmosphere at room temperature for 2 hours. Filter papers were then transferred to 5ml heart brain infusion and shaken at 37 degrees centigrade for minutes. 10ul was removed for sterility testing and the flasks incubated at 37 degrees centigrade for 18 hours. The flasks were inspected for growth and the growth.was checked on blood agar.
^1TUT& T1T RECEIVED 2 2 JJ 1988 17 Staphylococcus Pseudomonas Candida Concentration Control Test Control Test Control Test cfu/ml (10 log) 9 8 '7 6 4 3 growth kill Example 21 Whatman No. 4 filterpaper was impregnated with a solution of polyacrolein in methanol which had been polymerised by means of gamma-radiation) and dried in an oven at 70 degrees centigrade for 1 hour. The amount of impregnated polymeric antimicrobial was The impregnated filter paper was tested for antimicrobial activity and the results were recorded by comparing with a control filterpaper.
The following standard strains were used for testing: a) Staphylococcus aureus (Oxford) b) Pseudomonas ATCC c) Candida ATCC Dilutions were prepared in normal saline.
of each Jacterial dilution was applied to 1 square centimetre of test filter paper. The filter papers were maintained in a moist atmosphere at room temperature for 2 hours. Then the filter papers were transferred to heart brain infusion and shaken at 37 degrees centigrade for minutes. 1Oul was removed for sterility testing-and the 3 flasks incubated at 37 degrees centigrade for 18. hours. The flasks were inspected for growth and the growth was checked on blood agar.
LL f I E IV RECEl DD 2 2 JuJ 1988 18 Staphylococcus Pseudomonas Candida Concentration Control Test Control Test Control Test cfu/ml (10 log) 9 C 8 C '7 6 4 3 growth kill C contaminated Example 22 Whatman No. 4 filterpaper was impregnated with a solution of polyacrolein. In methanol, which has been prepared by polymerising 19.3g distilled acrolein in 58 g methanol in the presence of l.05g benzoylperoxide in a nitrogen atmosphere for 3 days at 70 degrees centigrade.
The amount of impregnated polymeric antimicrobial was 8%.
The impregnated filterpaper was tested for antimicrobial activity and the results were recorded by comparing with a control filterpaper.
The following standard strains were used for testing: a) Staphylococcus aureus (oxford) b) Pseudomonas ATCC c) Candida
ATCC
Dilutions were prepared in normal saline, of each bacterial dilution was applied to 1 square centimetre test filter paper. The filter papers were maintained in a moist atmosphere at room temperature* for 2 hours. Then, the filter papers were transferred to heart brain infusion and shaken at 37 degrees centigrade for minutes. The flasks were incubated at 37 degrees 0 ~2j Inc r RECEIVED 2 "2 J3i. 188 19 centigrade for 18 hours, inspected for growth and the growth was checked on blood agar.
Staphylococcus Pseudomonas Candida Concentration Control Test Control Test Control Test cfu/ml (10 log) 9 8 7 6 C growth kill C contaminated Example 23 Twice, in separate experiments, cotton wool was impregnated with a solution of polyacrolein in methanol which had been prepared by polymerizing 19.3g distilled acrolein in 58g methanol in the presence of 1.05 g benzoylperoxide in a nitrogen atmosphere for 3 days at degrees centigrade. The amount of impregnated, polymeric antimicrobial was 5% and 3.5% respectively. The impregnated cottonwools were tested for antimicrobial activity and the results were recorded by comparing with control cottonwool.
The following standard strains were used for testing; a) Staphylococcus Aureus (Oxford) b) Pseudomonas ATCC Dilutions were prepared in normal saline.
amounts of cottonwQol were weighed and placed in sterile bijoux bottles. The cottonwool was satutated with 30ul of 5 different bacterial dilutions. After 2 hours at room temperature, the cottonwool was transferred to of heart brain infusion /nd incubated for 18 hours at 37 rLcr uirr S* RcEi J J 20 degrees centigrade. Cultures were inspected for growth and growth was checked by plating on blood agar.
Staphylococcus Pseudomonas Concentration Control 3.5% 5% Control 3.5% cfu/ml (10 log) 4 103 2 1 growth kill It will be evident that these laboratory scale examples may be extended to industrial scale processes, for example, in which the substrate cellulose, prior to incorporation in, for example, tampons, diapers or medical cellulosic products is treated with acrolein vapour or acrolein solution and is then gamma-irradiated. Further, the process may be extended to the continuous (as well as batch) industrial processes in which cotton, cellulosic fibre or other fibres are treated with acrolein vapours or solution prior to weaving or making into a non-woven fabric.
Still further, the laboratory scale example may be extended to treating sheets, fabrics or cloths prior to making into clothes, drapes and other similar finished products. Still further, the example may be extended to treating the starting-materials or their final products such as ceramics, masonry, bricks, concrete, glass or plastics materials either prior to or after making these into their final fabricated forms.
.i t' ii i L i: i^ u U 4 RECEIVED 2 2 JUL 1988 21 Example 24 Many other substrates were treated with solutions containing active polymers, for example, gauze from bandages, non-woven fabric from sanitary napkins, cottonwool from tampons and always before microbiological testing, a control was used on the substrate which had been treated with 'the pure solvent (methanol). Substrttes which had been treated with the methanolic solutions of the polymers were always dried at 80 degrees centigrade/l.5 hours before 1 antimicrobial testing and as well, extracts were made with both methanol and physiological saline to test for the presence of monomer; this was found by HPLC and GC to be less than 10ppm at which the acrolein was found to be microbiologically inactive during our tests: Cotton (3.8769) with a 3% content of polyacrolein was agitated in saline (75ml) for 24 hours.
The saline extract was analysed by GLC carbowax 20M and on FID detector) which showed that the cotton contained less than 20ppm (the limit of detection).
The saline extract (50ml) was added to a solution of 2,4-dinitrophenylhydrazine (0.100g) in 2N hydrochloric acid (25ml). The resultant solution was extracted with chloroform (3 x 5ml). The combined organic fractions were then washed with 2N hydrochloric acid (2 x 5ml), water (2 x and dried (sodium sulphate). The chloroform was evaporated to dryness and the residue dissolved in acetonitrile (lml). Analysis of the acetonitrile by HPLC (C18 reverse phase, 70% aqueous mmethanol, UV detector at 245nm) showed that the cotton contained 2.4ppm of acrolein, Typically, substrates which were found to be microbiologically active, retained their activities after more than 6 months' standing at room temperature, The following are typical and additional testresults, executed similarly to examples 20-23: F. I I j 1 U 'I 4 -2 iRECENEoD 2 2 JUL 8e Example No. A i n StaphyloccOdCU S. 0 monas Candida 1* 2* 3 NT NT 4 NT
NT
6 NT 7 8 9 11** 12 NT NT 13 NT NT 14 NT NT NT NT 16 NT NT 17 NT NT 18 NT NT 19 NT NT NT not tested positive/active Tests were also carried out in phosphate buffers, adjusted with sodium hydroxide to give pHl's of 6, 7, 8 and 9, respectively; results against staphiococcus (Oxford) at levels L0 108 showed no differences in activities at the respective pHas.
Activities were also retained at the level of 25 ul heparinized blood cr urine, respectively (both human).
In another experiment, a methanolic solution was applied to spore strips of Bacillus subtlis var niger and left in contact at room temperature for 2 hours before transferring to heart brain infusion C n*)r s in 4* l i"ur Jle U W S* 49Tj 1 I- SRECEiVED 2 2 JUL f988 23 for IP hours/37 degrees centigrade. The cultures were inspected for growth and plated to blood agar the solution of polymer being active against the spores, whilst the ,iethanol-solvent was inactive under these conditions.
In separate experiments, 0.lg of cotton wool which had been coated with the polymer, was aseptically weighed into separate sterile bijoux bottles. The cotton ;-ool was then incubated with 0.5ml of dilutionir- of cultures of Erwinia carotovora (Important in soft, rot of potatoes or cabbages}, S.Aureus (important regarding bovine mastilis) and Salmonella dublin (important regarding bovine calf mortality), respectively. These were left at room temperature for 2 hours and then the cotton wool was transferred to TS3, an enriched nutrient broth and incubated at 32 degrees .entigrade, 37 degrees centigrade and 37 degrees centigrade, respectively.
The coating on the respective cotton wools killed the 3 organisms respectively, in the range i05-107/ml of pathogens.
In separate and similar experiments (except the media used was malt extract broth, Sabouraud dextrose agar, 0.1% peptone water as diluent), kills were achieved in the range 102-10 5 /ml of Aureobasidium pullurans (associated with black-slime on bathroom tiles and groutings) and Pycnoporus coccineus (associated with rotting in timbe rs) In 3 separate experiments, tests were also conducted for ahti-viral activities and found active in each case, using the following method for Herpes Simplex, Ente'ovirus, Echo 11 and Influenza PR8, respectively: a 10 /ml suspension of the viral particles was applied to cottonwool treated with the antimocrobial polymer, followed by centrifugation. 0.1 ml aliquots of the #Ii RECEVED 2 2 JUL 8 24 centrifugate were introduced into cultures of human embryonic fibroblasts or HeLa cells and the cytopathic effect noted.
Also active in a ptaservative test conducted over 14 days at pH 7.5 in glycerol-. -iethanolamine buffer, against Pseudomonas ATCC dilutions prepared in normal saline.
f "Staphylococcus", Pseudomonas" and "Candida" referred to herein are more specificically identified as: Staphlycoccus aureus NCTC 6571 Pseudomonas aeruginosa ATCC 27853 Candida albicans PMH 82/312 I c A& r ~r 1
Claims (9)
1. A process for rendering matter blocidal or biostatic, which process comprises applying to or incorporating in the matter a biocidally or biostatically effective amount of a polymer compound having the polymeric unit CH .CH--CH CH- 2 1 2 CHu CHio ;or this unit in a hydrated, hemi-acetal or acetal form of the formulae A 'S. S 0S* *SO k V., H CH CH Ro U ,,R
2-C Cu.H H~ ''OH (b) Lo H CH C H CMH CI 0 h"' C H 2 C H CMH CMI 1 453Y i i i i 26 0 CH 2 CH- CH 2 (e) CH CHCH CH CHCH CCH CH 0 C H 0 CH CH C CH CH- CH 2 CH HO OH HO OH (f) .I wherein R is hydrogen and xY is an integer of 1 or more; or a composition containing said polymeric compound. S: 2. A process as claimed in claim 1 wherein the composition o containing said polymeric compound is in the form of a solid, liquid, solution, gel, emulsion or suspension.
3. A process as claimed in claim 1 or claim 2 wherein the matter is water, water-containing compositions, food, cosmetics, toiletries, pharmaceuticals, oil or lubricants, cellulose, modified cellulose, regenerated cellulose, rayon, polymers of plastic materials, rubbers, ceramics, glass, silica, concrete, masonry or minerals. S4. A process as claimed in claim 3 wherein the polymers of plastic materials are vinyl polymers, acrylic polymers or polyesters. A process as claimed in claim 1 or claim 2 wherein the matter is in the form of airconditioner filters, aprons, bags for laundry, bandages, I tiles or grout, bricks, carpets, catheters or other related hospital instruments made from plastic or glass, clothing, food wraps, concrete, cottonballs or cotton tips, diapers, drapes, disposable cardboard or plastic food boxes, face masks, bed covers, inners of shoes, ironing board covers, nursing pads, paint, paper plates and cups, water reservoirs or swimming pool or water-treatment chemicals, rubbish bins, sanitary napkins or feminine hygiene tampons, shelving paper, shower curtains, teatowels, telephones, tents, tissues, handkerchiefs, toilet paper, toothbrushes, towels, wall paper, window awnings or other like structures made from canvas or plastic, wipes, tops, sponges, wood or wood-impregnants. 453y p 27
6. A polymeric biocidal or biostaric composition comprising a biocidally or biostatically effective amount of a polymer compound having the polymeric repeating unit CH 2 -CH-CH 2 -CH- CH CI or this unit in hydrated, hemi-acetal or acetal form of the formulae *too .9 o. *Voo CCH C H R 0 0 "D ~CH,CH C H C H I I CL CH 0O 0H (a H 2 H H ~H HO 0L CH1 O-,0H CE, CH 0 CH 12H CH2 C) 0 C H C 2 CH- CHCH-CH 2 C90C H -C H.C 0 CE H L r CH 2 C I E0 OH HO "O 1453y :~41 i- -I 28 wherein R is hydrogen and x is an integer of 1 or more; or a composition containing said polymeric compound, incorporated in or bound to a substrate or substrate material.
7. A composition as claimed in claim 6 wherein the substrate is selected from cellulose, modified cellulose, regenerated cellulose, rayon, polymers of plastic materials, rubbers, ceramics, glass, silica, concrete, masonry, minerals and earths.
8. A composition as claimed in claim 7 wherein the polymers of plastic materials are vinyl polymers, acrylic polymers or polyesters.
9. A process for preparing a composition as claimed in any one of claims 6 to 8 which comprises polymerizing acrolein or a derivative thereof in the presence of the substrate or substrate material. A process as claimed in claim 9 wherein the process is carried i: 1 out in the presence of a polymerization inducing agent comprising an ionic catalyst, gamma radiation, a free radical catalyst, ultraviolet radiation or electron beam radiation or a combination thereof,
11. A process for rendering matter biocidal or biostatic, substantially as hereinbefore described with reference to any one of I"'i Examples 14 to 24. hereinbefore described with reference to any one of Examples 14 to 24.
13. A process of preparing a composition of matter as claimed in claim 12, substantially as hereinbefore described with reference to any one of E':amples 14 to 24. DATED this FIRST day of AUGUST 1991 Biopolymers Limited Patent Attorneys for the Applicant SPRUSON FERGUSON /KXW:1453y C>, I RE C E I VU9 22 j Iq8 "ABSTRACT" Polymeric compounds having a polyacrolein sub unit in aldehyde, hydrated, hemi acetal or acetal form are provided which have biocidal or biostatic properties. The polymeric compound may-be used to treat, or be included in, a wide range of products. 14:25'N T
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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AUPH965786 | 1986-12-23 | ||
AUPH9657 | 1986-12-23 |
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Publication Number | Publication Date |
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AU1086488A AU1086488A (en) | 1988-07-15 |
AU616166B2 true AU616166B2 (en) | 1991-10-24 |
AU616166C AU616166C (en) | 1993-07-15 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3635898A (en) * | 1969-07-03 | 1972-01-18 | Gaf Corp | Process for polymerization of acrolein |
US4016127A (en) * | 1971-07-06 | 1977-04-05 | Rohm And Haas Company | Emulsion copolymers of acrolein and their use in treating leather |
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3635898A (en) * | 1969-07-03 | 1972-01-18 | Gaf Corp | Process for polymerization of acrolein |
US4016127A (en) * | 1971-07-06 | 1977-04-05 | Rohm And Haas Company | Emulsion copolymers of acrolein and their use in treating leather |
Also Published As
Publication number | Publication date |
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US5290894A (en) | 1994-03-01 |
MY102278A (en) | 1992-05-15 |
JPH02501750A (en) | 1990-06-14 |
NO883639L (en) | 1988-10-12 |
DK174224B1 (en) | 2002-09-30 |
ZA879640B (en) | 1989-09-27 |
AU1086488A (en) | 1988-07-15 |
EP0339044B1 (en) | 1994-02-23 |
NZ222979A (en) | 1990-09-26 |
KR950008720B1 (en) | 1995-08-04 |
DE3789150T2 (en) | 1994-07-28 |
EP0339044A1 (en) | 1989-11-02 |
DK469788A (en) | 1988-10-24 |
ATE101860T1 (en) | 1994-03-15 |
PH23983A (en) | 1990-02-09 |
KR890700617A (en) | 1989-04-26 |
EP0339044A4 (en) | 1990-05-14 |
DE3789150D1 (en) | 1994-03-31 |
NO883639D0 (en) | 1988-08-16 |
IN166555B (en) | 1990-06-09 |
HK103394A (en) | 1994-10-07 |
NO173737C (en) | 1994-01-26 |
DK469788D0 (en) | 1988-08-22 |
JP2857756B2 (en) | 1999-02-17 |
CA1320128C (en) | 1993-07-13 |
NO173737B (en) | 1993-10-18 |
WO1988004671A1 (en) | 1988-06-30 |
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